Controlling undesirable plant growth using naphthindazole-4,9-quinones

ABSTRACT

Naphthindazole-4,9-quinones of the formula ##STR1## where R 1  to R 5  have the meanings given in the disclosure, and their use for combating unwanted plant growth.

The present invention relates to naphthindazole-4,9-quinones and use thereof for controlling undesirable plant growth.

It has already been disclosed that indazolequinone derivatives have herbicidal properties (DE-A-2,107,053). Furthermore, naphthindazole-4,9-quinones are known from Chem. Ber. 97 (1964), 2555, and from Liebigs Ann. Chem. (1985), 251, but nothing is said about their use.

We have found that naphthindazole-4,9-quinones of the formula ##STR2## where R¹ is hydrogen, C₁ -C₁₀ -alkyl, C₂ -C₁₀ -alkenyl, C₂ -C₁₀ -alkynyl, C₁ -C₁₀ -haloalkyl, C₁ -C₁₀ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, C₁ -C₄ -alkylcarbonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylsulfonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl,di(C₁ -C₄ -alkyl)aminocarbonyl-C₁ -C₄ -alkyl, halogen-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substituted heteroaryl of one or two nitrogen atoms, unsubstituted or halogen-, hydroxyl-, nitro-, amino-, C.sub. 1 -C₄ -alkylamino-, di-C₁ -C₄ -alkylamino-, cyano-, C₁ -C₄ -alkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -haloalkoxy-, C₁ -C₄ -haloalkyl-, C₁ -C₄ -alkylthio- or C₁ -C₄ -haloalkylthio-substituted phenyl or unsubstituted or halogen-substituted benzyl and

R², R³, and R⁴ and R⁵ are each independently of the other hydrogen, halogen, nitro, cyano, hydroxyl, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkoxy, C₁ -C₅ -alkylthio, C₁ -C₅ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, carboxyl , C₂ -C₆ -alkoxycarbonyl C₂ -C₆ -alkanoyloxy, C₂ -C₆ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di(C₁ -C₄ -alkyl)aminocarbonyl, or unsubstituted or halogen-, trifluoromethyl-,nitro-, cyano -, amino-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkylthio- or C₁ -C₅ -haloalkylthio-substituted phenyl or heteroaryl

and in addition

R³ and R⁴ together with the two carbon atoms of the phenyl ring to which they are bonded form a heterocyclic ring or an unsubstituted or halogen-, nitro-, cyano-, amino-, hydroxyl-, trifluoromethyl-, C₁ -C₅ -alkyl-, C₁ -C₅ -alkoxy-, C₁ -C₅ -haloalkylthio-, C₁ -C₅ -haloalkoxy- or C₁ -C₅ -alkylthio-substituted benzene or naphthalene ring,

have good herbicidal properties and are selectively active with respect to crop plants.

In the formula Ia, the radicals R¹, R², R³, R⁴ and R⁵ have the following meanings:

R¹ : hydrogen, C₁ -C₁₀ -alkyl, preferably C₁ -C₄ -alkyl, C₂ -C₁₀ -alkenyl, preferably C₂ -C₄ -alkenyl, C₂ -C₁₀ -alkynyl, preferably C₂ -C₄ -alkynyl, C₁ -C₁₀ -hydroxyalkyl, preferably C₁ -C₄ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl, preferably C₂ -C₆ -alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, preferably C₂ -C₆ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, preferably C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkylcarbonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylsulfonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl,di(C₁ -C₄ -alkyl)aminocarbonyl-C₁ -C₄ -alkyl, halo-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substituted heteroaryl of one or two nitrogen atoms, e.g. pyrimidyl, pyridyl or imidazolyl, unsubstituted or halogen-, hydroxyl-, nitro-, amino-, C₁ -C₄ -alkylamino-, di-C₁ -C₄ -alkylamino-, cyano-, C₁ -C₄ -alkyl-, C₁ -C₄ -haloalkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -haloalkoxy-,C₁ -C₄ -alkylthio- or C₁ -C₄ -haloalkylthio-monosubstituted or polysubstituted phenyl, unsubstituted or halogen-monosubstituted or -polysubstituted (in the phenyl) benzyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, tert.amyl, n-hexyl, pentyl-3, 1,2-dimethyl-n-propyl, 1,3-dimethyl-n-butyl, 1-ethyl-2-methyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1,2-dimethyl-4-hexyl, allyl, methallyl, crotyl, 2 -ethylhex-2-enyl, hex-5-enyl, 2-methylbut-2-enyl, 2-methylbut-3-enyl, but-1-en-3-yl, 2-methylbut-1-en-4-yl, 2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl, propargyl, but-1-yn-3-yl, but-2-ynyl, 2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl,2-chloro-sec.-butyl,2-chloroisobutyl, 2-fluoro-sec.-butyl, 2-fluoroisobutyl, 2-fluoroisopropyl, chloro-tert.-butyl, 2,2,2-trifluoroethyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxyisopropyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, 2-hydroxyisobutyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxy-n-propyl, 2-methoxyisopropyl, 3-methoxy-n-butyl, 1-methoxy-sec.-butyl, methoxy-tert.-butyl, ethoxy-tert.-butyl, 2-methoxy-n-butyl, 4-methoxy-n-butyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-methylmercaptoethyl, 2-ethylmercaptoethyl, 3-methylmercapto-n-propyl, 3-methylmercapto-n-butyl, 1-methylmercapto-sec.-butyl, methylmercapto-tert.butyl, 2-methylmercapto-n-butyl, phenyl, 4-chlorophenyl,3,4-dichlorophenyl, o-, m- or p-tert-butylphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-methylphenyl, 4-methoxy-3-chlorophenyl, 2-methyl-4-chlorophenyl, benzyl,2,6-dichlorobenzyl,2-chloro-6-fluorobenzyl, 2,6-difluorobenzyl or o-, m- or p-chlorobenzyl.

R², R³, R⁴, R⁵ : hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, nitro, cyano, hydroxyl, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, preferably C₁ -C₄ -alkyl, C₁ -C₅ -haloalkyl, preferably C₁ -C₃ -haloalkyl, C₁ -C₅ -alkoxy, preferably C₁ -C₃ -alkoxy, C₁ -C₅ -haloalkoxy, preferably C₁ -C₃ -haloalkoxy, C₁ -C₅ -alkylthio, preferably C₁ -C₃ -alkylthio, C₁ -C₅ -haloalkylthio, preferably C₁ -C₃ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, preferably C₂ -C₆ -alkoxyalkyl, carboxyl, C₂ -C₆ -alkoxycarbonyl, preferably C₂ -C₄ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, preferably C₂ -C₄ -alkanoyloxy, C₃ -C₆ -haloalkanoyloxy, preferably C₂ -C₄ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di(C₁ -C₄ -alkyl)-aminocarbonyl, unsubstituted or halogen-, preferably chlorine- or fluorine-, trifluoromethyl-, nitro-, cyano-, amino-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkylthio- or C₁ -C₅ -haloalkylthio-substituted phenyl or heteroaryl, preferably pyridyl, pyrimidyl, thienyl, furyl or benzimidazolyl, e.g. methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, diisopropylamino, methylethylamino, n-, iso- or tert.butylamino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, tert.-amyl, n-hexyl, pentyl-3, 1,2-dimethyl-n-propyl, 1,3-dimethyl-n-butyl, 1-ethyl-2-methyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1,2-dimethyl-n-hexyl, allyl, methallyl, crotyl, 2-ethylhex-2-enyl, hex-5-enyl, 2-methylbut-2-enyl, 2-methylbut-3-enyl,but-1-en-3-yl,2-methylbut-1-en-4-yl, 2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl, propargyl, but-1-yn-3-yl, but-2-ynyl, fluoromethyl, chloromethyl, trifluoromethyl, difluoromethyl, trichloromethyl, dichloromethyl, 2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloroisopropyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 2-fluoroisopropyl, 3-fluoro-n-propyl, 2-fluoroethyl, methoxy, ethoxy, n- or isopropoxy, n-, iso- or tert.-butoxy, pentoxy, difluoromethoxy, trifluoromethoxy, trichloromethoxy, methylthio, ethylthio, n- or isopropylthio, n-, iso- or tert.-butylthio, difluoromethylthio, trifluoromethylthio, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 3-methoxy-n-propyl, 2-methoxyisopropyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 2-ethoxyisopropyl, methoxycarbonyl, ethoxycarbonyl, n- or isopropoxycarbonyl, n-, iso- or tert.-butoxycarbonyl, 2-methoxyethoxycarbonyl, ethoxymethoxycarbonyl, 2-ethoxyethoxycarbonyl, phenyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, 2,4-difluorophenyl, 2,4-p-trifluoromethylphenyl, 2-, 3-and 4-nitrophenyl, 2-, 3- and 4-cyanophenyl, 2-, 3-and 4-aminophenyl, 2-, 3 - and 4-methoxyphenyl,2,4-dimethoxyphenyl,2,4,5-trimethoxyphenyl, 2-, 3- and 4-thiomethylphenyl, heteroaryl such as pyrid-2-yl, pyrid-3-yl, pyrid-4-yl, thien-2-yl, thien-3-yl, fur-2-yl, fur-3-yl, benzimidazol-2-yl,3-chloropyrid-6-yl,2-methylfur-5-yl, 2-methylthien-5-yl and 4,6-dimethylpyrimid-2-yl, acetyl, propionyl, butyryl, isobutyryl, valeroyl, isovaleroyl, pivaloyl, chloroacetyl, dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, 3,3,3-trifluoropropionyl, pentafluoropropionyl, 2-chloropropionyl, 2,2-dichloropropionyl, 2-fluoropropionyl or 2,2-difluoropropionyl.

R³ and R⁴ may also form together with the two carbon atoms of the phenyl ring to which they are bonded an unsubstituted or fluorine-, chlorine-, bromine-, nitro-, cyano-, amino-, hydroxyl-, trifluoromethyl-, C₁ -C₅ -alkyl-, preferably C₁ -C₃ -alkyl-, C₁ -C₅ -alkoxy-, C₁ -C₅ -haloalkylthio-, C₁ -C₅ -haloalkoxy- or C₁ -C₅ -alkylthio-, preferably C₁ -C₃ -alkylthio-, substituted benzene or naphthalene ring.

Examples of heterocyclic rings formed by R³ and R⁴ together with the two carbon atoms of the phenyl ring to which they are bonded are 1,4-dioxane, 1,3-dioxolane, pyrazole, indole, thiophene, triazole and piperazine. Examples of the corresponding substituted rings are 2,2-dimethyl-1,3-dioxalane, 1-methylpyrazole, 1-methylindole, N,N'-dimethylpiperazine,2,2-diphenyl-1,3-dioxolane, and 2-oxo-1,3-dioxolane.

Naphthindazole-4,9-quinones of the formula Ia where R¹ is C₁ -C₄ -alkyl or C₂ -C₄ -alkenyl are preferred. Preference is further given to those compounds of the formula Ia where the substituents R² to R⁵ are each independently of the others hydrogen, hydroxyl, halogen, nitro, cyano, amino, C₁ -C₄ alkylamino or di-C₁ -C₄ -alkylamino. Preference is given in particular to compounds where R² to R⁵ are each hydrogen, hydroxyl or halogen.

The naphthindazole-4,9-quinones of the formula ##STR3## where R¹, R², R³, R⁴ and R⁵ are each as defined for the formula Ia, with the proviso that R¹ is not hydrogen or methyl, are novel.

The naphthindazole-4,9-quinones of the formula I are obtained by reacting the 5-arylmethylpyrazol-4-yl carbonyl halides of the formula ##STR4## where R¹, R², R³, R⁴ and R⁵ are each as defined above and Hal is halogen, in an inert solubilizer in the presence of a Friedel-Crafts catalyst, and converting the resulting compounds of the formula ##STR5## where R¹, R², R³, R⁴ and R⁵ are each as defined above, in the presence of a diluent with oxidizing agents into the naphthindazole-4,9-quinones of the formula I.

Suitable inert solubilizers for this purpose are carbon disulfide, nitromethane, nitrobenzene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, sulfolane, trichloroethylene and 1,1,1-trichloroethane.

Suitable Friedel-Crafts catalysts are aluminum trichloride, boron trifluoride, tin tetrachloride, titanium tetrachloride, zinc chloride, boron trichloride, trifluoroacetic acid, sulfuric acid, aluminum bromide, gallium chloride, iron(III) chloride, antimony pentachloride, antimony trichloride and zirconium tetrachloride. The amount of catalyst is from 5 to 500, preferably from 100 to 250, mol %, based on starting acid chloride of the formula II.

The reaction advantageously takes place at from 0° to 150° C.

The oxidation of compounds III is advantageously carried out in an inert diluent, such as acetic acid or alcoholic alkali metal hydroxide solution, in the presence or absence of water, at from 0° to 120° C. Suitable oxidizing agents are hydrogen peroxide and chromium(IV) oxide.

The oxidation is advantageously carried out by dissolving the starting compounds III in dilute, aqueous-alcoholic solutions of alkali metal hydroxides at temperatures of from 0° C. to 120° C., preferably from 50° C. to 100° C., and adding excess aqueous hydrogen peroxide solution. The reaction will in general have ended after 4-8, but not more than 24, hours. The solid end product is filtered off with suction and may be recrystallized or chromatographed for purification.

The synthesis of the 5-arylmethylpyrazol-4-yl carbonyl halides II can be effected in a conventional manner in accordance with the following scheme: ##STR6##

The naphthindazole-4,9-quinones of the formula I are likewise obtained on reacting substituted 1,4-naphthoquinones of the formula ##STR7## where R², R³, R⁴ and R⁵ are each as defined above, with diazomethane in the presence of inert diluents, for example aliphatic or alicyclic ethers, oxidizing the resulting compounds of the formula ##STR8## where R², R³, R⁴ and R⁵ are each as defined above, in an inert diluent and alkylating the resulting naphthindazole-4,9-quinones of the formula ##STR9## where R², R³, R⁴ and R⁵ are each as defined above, with an alkylating agent of the formula

    R.sup.1 -X                                                 (VII)

where

R¹ is as defined above and

X is p-toluenesulfonate, mesylate, brosylate, halogen or a group of the formula ##STR10## where R¹ is as defined above, in a diluent in the presence of a base at from -30° C. to +100° C.

The reaction of the 1,4-naphthoquinones IV with diazomethane can be carried out in a conventional manner (Houben-Weyl, Methoden der org. Chemie, volume 7/3a, page 553 (1977)). The oxidation of compounds V is possible inter alia with hydrogen peroxide, chromium(VI) oxide or atmospheric oxygen in an inert diluent, such as dilute acetic acid or methyl t-butyl ether.

The alkylation of the naphthindazole-4,9-quinones VI with the alkylating agent VII takes place in a conventional manner in a diluent, for example water or acetone or mixtures thereof, in the presence of a base, such as alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal carbonates or alkali metal or alkaline earth metal bicarbonates. It is preferable to work at from 10° to 30° C.

All the other starting compounds and reaction products whose preparation has not been described in detail are either known or can be prepared by known principles.

Preparation Examples EXAMPLE 1 ##STR11##

A suspension of 20.6 g (0.13 mol) of 1,4-naphthoquinone in 500 ml of methyl t-butyl ether is admixed under a protective gas atmosphere at 0° C. with 400 ml of a 3.5×10⁻⁴ M solution (0.14 mol) of diazomethane in diethyl ether. After the addition has ended, the suspension is heated to room temperature, and air is passed through the reaction mixture overnight. The precipitate formed is then filtered off with suction, washed with 100 ml of methyl t-butyl ether and stirred into 75 ml of hot ethanol. It is filtered off with suction, washed with 100 ml of ethanol and dried.

Yield: 12.1 g (47% of theory)

Melting point: 180° C. decomposition

EXAMPLE 2 ##STR12##

6.0 g (0.03 mol) of naphthindazole-4,9-quinone (Example 1) are suspended in 100 ml of 80% strength aqueous acetone and admixed at room temperature in succession with 3.2 g (0.03 mol) of sodium carbonate and 7.3 g (0.06 mol) of 1-bromo-2-propene. The mixture is stirred overnight and then refluxed for three hours. It is cooled down, admixed with a further 1.1 g (0.01 mol) of sodium carbonate and 2.4 g (0.02 mol) of 1-bromo-2-propene and refluxed for a further two hours. It is then concentrated under reduced pressure and extracted four times with 100 ml of dichloromethane each time. The combined extracts are dried over sodium sulfate and concentrated. The crystalline residue is chromatographed over silica gel (mobile phase: cyclohexane/ethyl acetate) to obtain 4.6 g (64% of theory) of 1-(propen-2-yl)naphthindazole-4,9-quinone of melting point 105-108° C.

EXAMPLE 3 ##STR13##

(a) 1.25 g (0.005 mol) of 5-(4-chlorophenylmethyl)-1-methylpyrazol-4-yl carboxylic acid (preparation: G. Menozzi, L. Mosti and P. Schenone, J. Heterocycl. Chem. 24 (1987), 1669) are dissolved in 2 ml of thionyl chloride and refluxed for one hour. Excess thionyl chloride is then removed under reduced pressure (12 mmHg), the residue is taken up in 20 ml of diethyl ether, and the mixture is stirred with 2.0 g of active charcoal. The mixture is filtered after 30 minutes, the filtrate is concentrated under reduced pressure to give 1.25 g (93% of theory) of acid chloride as a colorless oil.

(b) 1.25 g (4.6 mmol) of 5-(4-chlorophenylmethyl)-1-methylpyrazol-4-yl carbonyl chloride are dissolved in 5 ml of nitromethane and added to a 0° C. solution of 1.85 g (14 mmol) of aluminum chloride in 20 ml of nitromethane. The mixture is stirred at room temperature overnight and then poured into a mixture of 50 g of ice and 20 ml of concentrated hydrochloric acid. The organic phase is separated off, the aqueous phase is extracted twice more with 50 ml of dichloromethane each time and the combined extracts are dried over sodium sulfate. Removing the solvent under reduced pressure leaves 1.10 g (100% of theory) of 6-chloro-9-hydro-1-methylnaphthindazol-4-one of melting point >270° C.

¹ H--NMR (250 MHz, DMSO--d₆) 4.05 (s; 3H), 4.45 (s; 2H), 7.35 (dd, J=9.2 and 0.2 Hz; 1H), 7.90 (d,J=9.0 Hz; 1H), 8.20 (d, J=0.2 Hz; 1H), 8.45 (s; 1H)

(c) 1.10 g (4.6 mmol) of 6-chloro-9-hydro-l-methylnaphthindazol-4-one are dissolved in a mixture of 10 ml of 10% strength sodium hydroxide solution and 50 ml of methanol by heating (80° C.). The solution is cooled down to 60° C., and 5 ml of a 30% strength solution of hydrogen peroxide are added. The mixture is stirred at room temperature overnight, and the precipitated quinone is then filtered off with suction, giving 0.85 g (57% of theory) of 1-methyl-6-chloronaphthindazol-4,9-quinone of melting point 219° C.

¹ H-NMR (250 MHz, CDCl₃) 4.35 (s; 3H), 7.72 (d, J=9.0 Hz; 1H), 8.05 (s; 1H), 8.18 (s; 1H), 8.18 (d, J=9.0 Hz; 1H).

The following compounds of the formulae I and Ia can be obtained in a similar manner:

    __________________________________________________________________________     Ex. no. R.sup.1          R.sup.2 -R.sup.5            Melting point                                                          [°C.]     __________________________________________________________________________     4       CH.sub.3         H                           181     5       CH.sub.2 CH.sub.3                              H                           151-152     6       isopropyl        H                           126     7       n-propyl         H     8       n-butyl          H                            69     9       t-butyl          H                           152     10      2-pentyl         H                           164     11      cyclopentyl      H     12      cyclohexyl       H                           148     13      CH.sub.2CF.sub.3 H                           171     14      CH.sub.2OH       H     15      CH.sub.2CH.sub.2OH                              H                           158     16              ##STR14##       H                           109     17              ##STR15##       H                           116     18              ##STR16##       H                           179     19              ##STR17##       H                           155     20      CH.sub.2COOC.sub.2 H.sub.5                              H                           149     21      CH.sub.2COOH     H     22              ##STR18##       H     23              ##STR19##       H     24              ##STR20##       H     25      CH.sub.2 CH.sub.2SCH.sub.3                              H     26      CH.sub.2SCH.sub.3                              H     27      CH.sub.2CCH      H                           193     28      CH.sub.2CCBr     H     29      phenyl           H                           221     30      benzyl           H                           154     31      2-(4,6-dimethylpyrimidinyl)                              H                           237     32      2-pyridinyl      H                           221     33      2-(2-imidazoline)                              H     34      2,4-dichlorophenyl                              H     35      2,4,6-trichlorophenyl                              H     36      4-fluorophenyl   H     37      2,4-difluorophenyl                              H     38      2,4,6-trifluorophenyl                              H     39      4-methoxyphenyl  H     40      2,4-dimethoxyphenyl                              H     41      4-thiomethylphenyl                              H     42      4-trifluoromethylphenyl                              H     __________________________________________________________________________     Example no.             R.sup.1          R.sup.2 R.sup.3                                            R.sup.4                                                  R.sup.5 Melting point                                                          [°C.]     __________________________________________________________________________     43      CH.sub.3         F       H     H     H       195     44      CH.sub.3         H       F     H     H     45      CH.sub.3         H       H     F     H       173     46      CH.sub.3         H       H     H     F     47      CH.sub.3         Cl      H     H     H     48      CH.sub.3         H       Cl    H     H       219     49      CH.sub.3         H       H     Cl    H       226     50      CH.sub.3         H       H     H     Cl     51      CH.sub.3         Br      H     H     H     52      CH.sub.3         H       H     H     Br      190-192     53      CH.sub.3         Cl      H     H     Cl     54      CH.sub.3         H       Cl    H     Cl      230     55      CH.sub.3         H       Cl    Cl    H     56      CH.sub.3         F       H     H     F     57      CH.sub.3         H       F     H     F     58      CH.sub.3         H       F     F     H     59      CH.sub.3         OH      H     H     H       190     60      CH.sub.3         H       OH    H     H     61      CH.sub.3         H       H     OH    H     62      CH.sub.3         H       H     H     OH      212     63      CH.sub.3         OH      H     H     OH      224-227     64      CH.sub.3         OCH.sub.3                                      H     H     H     65      CH.sub.3         H       OCH.sub.3                                            H     H       193     66      CH.sub.3         H       H     OCH.sub.3                                                  H       173     67      CH.sub.3         H       H     H     OCH.sub.3                                                          230     68      CH.sub.3         OCH.sub.3                                      H     CH.sub.3                                                  H       212-213     69      CH.sub.3         OH      H     H     OCH.sub.3     70      CH.sub.3         OCH.sub.3                                      H     H     OH     71      CH.sub.3         OCH.sub.3                                      OCH.sub.3                                            H     OCH.sub.3     72      CH.sub.3         OH      OCH.sub.3                                            H     OCH.sub.3     73      CH.sub.3         OCH.sub.3                                      H     OCH.sub.3                                                  H       212     74      CH.sub.3         OCH.sub. 3                                      H     OCH.sub.3                                                  OH     75      CH.sub.3         OH      H     OCH.sub.3                                                  H       208     76      CH.sub.3         H       OCH.sub.3                                            H     OCH.sub.3     77      CH.sub.3         H       OCH.sub.3                                            H     OH     78      CH.sub.3         H       OCH.sub.2CH.sub.2 O                                                  H     79      CH.sub.3         H       OCH.sub.2O  H       252     80      CH.sub.3         H       OH    OH    H     81      CH.sub.3         SCH.sub.3                                      H     H     H     82      CH.sub.3         H       SCH.sub.3                                            H     H     83      CH.sub.3         H       H     SCH.sub.3                                                  H     84      CH.sub.3         H       H     H     SCH.sub.3     85      CH.sub.3                               ##STR21##                                      H     H     H       220     86      CH.sub.3         H       H     H                                                   ##STR22##     87      CH.sub.3         CH.sub.3                                      H     H     H     88      CH.sub.3         H       CH.sub.3                                            H     H       177     89      CH.sub.3         H       H     CH.sub.3                                                  H       136     90      CH.sub.3         H       H     H     CH.sub.3                                                          218     91      CH.sub.3         CH.sub.3                                      H     H     CH.sub.3                                                          143     92      CH.sub.3         CF.sub.3                                      H     H     H     93      CH.sub.3         H       CF.sub.3                                            H     H     94      CH.sub.3         H       H     CF.sub.3                                                  H     95      CH.sub.3         H       H     H     CF.sub.3     96      CH.sub.3         H       CH.sub.3                                            H     OH      154     97      CH.sub.3         OH      H     CH.sub.3                                                  H       175     98      CH.sub.3         H       C.sub.4 H.sub.4                                                  OH      288     99      CH.sub.3         H       C.sub.4 H.sub.4                                                  H     100     CH.sub.3         OH      C.sub.4 H.sub.4                                                  H     101     CH.sub.3         H       C.sub.4 H.sub.4                                                   ##STR23##                                                          253     102     CH.sub.3                               ##STR24##                                      C.sub.4 H.sub.4                                                  H       231     103     CH.sub.3         F       C.sub.4 H.sub.4                                                  OH     104     CH.sub.3         NO.sub.2                                      H     H     H     105     CH.sub.3         H       H     H     NO.sub.2     106     CH.sub.3         NH.sub.2                                      H     H     H     107     CH.sub.3         H       H     H     NH.sub.2     108     CH.sub.3                               ##STR25##                                      H     H     H     109     CH.sub.3         H       H     H                                                   ##STR26##     110     CH.sub. 3        CN      H     H     H     111     CH.sub.3         H       CN    H     112     CH.sub.3         H       H     H     CN     113     CH.sub.3         C.sub.6 H.sub.5                                      H     H     H     114     CH.sub.3         H       C.sub.6 H.sub.5                                            H     H       185     115     CH.sub.3         H       H     C.sub.6 H.sub.5                                                  H     116     CH.sub.3         H       H     H     C.sub.6 H.sub.5     117     CH.sub.3         COOCH.sub.3                                      H     H     H     118     CH.sub.3         H       H     H     COOCH.sub.3     119     CH.sub.3         COOH    H     H     H     120     CH.sub.3         H       H     H     COOH     121     CH.sub.3         CONHCH.sub.3                                      H     H     H     122     CH.sub.3         H       H     H     CONHCH.sub.3     123     CH.sub.3         CON(CH.sub.3).sub.2                                      H     H     H     124     CH.sub.3         H       H     H     CON(CH.sub.3).sub.2     125     C.sub.6 H.sub.5  OH      H     H     OH      208     126     C.sub.6 H.sub.5  OH      H     H     H     127     C.sub.6 H.sub.5  H       H     H     OH     128     C.sub.6 H.sub.5  F       H     H     H     129     C.sub.6 H.sub.5  H       H     F     H     130     C.sub.6 H.sub.5  H       H     H     F     131     C.sub.6 H.sub.5  Cl      H     H     H     132     C.sub.6 H.sub.5  H       H     H     Cl     133     C.sub. 6 H.sub.5 OH      H     OCH.sub.3                                                  H     134     C.sub.6 H.sub.5  OCH.sub.3                                      H     OH    H     135     C.sub.6 H.sub.5  H       OCH.sub.3                                            H     OH     136     C.sub.6 H.sub.5  CF.sub.3                                      H     H     H     137     C.sub.6 H.sub.5  H       H     CF.sub.3                                                  H     138     C.sub.6 H.sub.5  H       H     H     CF.sub.3     139     C.sub.6 H.sub.5  NH.sub.2                                      H     H     H     140     C.sub.6 H.sub.5  H       H     NH.sub.2                                                  H     141     C.sub.6 H.sub.5  H       H     H     NH.sub.2     142     C.sub.6 H.sub.5  H       NO.sub.2                                            H     H     143     C.sub.6 H.sub.5  NO.sub.2                                      H     H     H     144     C.sub.6 H.sub.5  F       F     H     H     145     isopropyl        H       CF.sub.3                                            H     H     146     isopropyl        H       H     CF.sub.3                                                  H     147     isopropyl        H       H     H     CF.sub.3     148     isopropyl        H       CH.sub.3                                            H     OH     149     isopropyl        OH      H     CH.sub.3                                                  H     150     isopropyl        H       C.sub.4 H.sub.4                                                  OH     151     isopropyl        H       C.sub.4 H.sub.4                                                  H     152     isopropyl        OH      C.sub.4 H.sub.4                                                  H     153     isopropyl        H       C.sub.4 H.sub.4                                                   ##STR27##     154     isopropyl                               ##STR28##                                      C.sub.4 H.sub.4                                                  H     155     isopropyl        F       C.sub.4 H.sub.4                                                  OH     156     isopropyl        NO.sub.2                                      H     H     H     157     isopropyl        H       H     H     NO.sub.2     158     isopropyl        NH.sub.2                                      H     H     H     159     isopropyl        H       H     H     NH.sub.2     160     isopropyl                               ##STR29##                                      H     H     H     161     isopropyl        H       H     H     NHCOCH.sub.3     162     isopropyl        CN      H     H     H     163     isopropyl        H       CN    H     H     164     isopropyl        H       H     H     CN     165     isopropyl        C.sub.6 H.sub.5                                      H     H     H     166     isopropyl        H       C.sub.6 H.sub.5                                            H     H     167     isopropyl        H       H     C.sub.6 H.sub.5                                                  H     168     isopropyl        H       H     H     C.sub.6 H.sub.5     169     isopropyl        COOCH.sub.3                                      H     H     H     170     isopropyl        H       H     H     COOCH.sub.3     171     isopropyl        F       H     H     H     172     isopropyl        H       F     H     H     173     isopropyl        H       H     F     H     174     isopropyl        H       H     H     F     175     isopropyl        Cl      H     H     H     176     isopropyl        H       Cl    H     H     177     isopropyl        H       H     Cl    H     178     isopropyl        H       H     H     Cl     179     isopropyl        Br      H     H     H     180     isopropyl        F       H     H     Br     181     isopropyl        Cl      H     H     Cl     182     isopropyl        H       Cl    H     Cl     183     isopropyl        H       Cl    Cl    H     184     isopropyl        F       H     H     F     185     isopropyl        H       F     H     F     186     isopropyl        H       F     F     H     187     isopropyl        OH      H     H     H     188     isopropyl        H       OH    H     H     189     isopropyl        H       H     OH    H     190     isopropyl        H       H     H     OH     191     isopropyl        OH      H     H     OH     192     isopropyl        OCH.sub.3                                      H     H     H     193     isopropyl        H       OCH.sub.3                                            H     H       176     194     isopropyl        H       H     OCH.sub.3                                                  H       160     195     isopropyl        H       H     H     OCH.sub.3     196     isopropyl        OCH.sub.3                                      H     H     OCH.sub.3     197     isopropyl        OH      H     H     OCH.sub.3     198     isopropyl        OCH.sub.3                                      H     H     OH     199     isopropyl        OCH.sub.3                                      OCH.sub.3                                            H     OCH.sub.3     200     isopropyl        OH      OCH.sub.3                                            H     OCH.sub.3     201     isopropyl        OCH.sub.3                                      H     OCH.sub.3                                                  OCH.sub.3     202     isopropyl        OCH.sub.3                                      H     OCH.sub.3                                                  OH     203     isopropyl        OH      H     OCH.sub.3                                                  H     204     isopropyl        H       OCH.sub.3                                            H     OCH.sub.3     205     isopropyl        H       OCH.sub.3                                            H     OH     206     isopropyl         H      OCH.sub.2CH.sub.2 O                                                  H     207     isopropyl        H       OCH.sub.2O  H     208     isopropyl        H       OH    OH    H     209     isopropyl        SCH.sub.3                                      H     H     H     210     isopropyl        H       SCH.sub.3                                            H     H     211     isopropyl        H       H     SCH.sub.3                                                  H     212     isopropyl        H       H     H     SCH.sub.3     213     isopropyl                               ##STR30##                                      H     H     H     214     isopropyl        H       H     H                                                   ##STR31##     215     isopropyl        CH.sub.3                                      H     H     H     216     isopropyl        H       CH.sub.3                                            H     H     217     isopropyl        H       H     CH.sub.3                                                  H     218     isopropyl        H       H     H     CH.sub.3     219     isopropyl        CH.sub.3                                      H     H     CH.sub.3     220     isopropyl        CF.sub.3                                      H     H     H     221     isopropyl        COOH    H     H     H     222     isopropyl        H       H     H     COOH     223     isopropyl        CONHCH.sub.3                                      H     H     H     224     isopropyl        H       H     H     CONHCH.sub.3     225     isopropyl        CON(CH.sub.3).sub.2                                      H     H     H     226     isopropyl        H       H     H     CON(CH.sub.3).sub.2     227     CH.sub.2CCH      OH      H     H     H     228     CH.sub.2CCH      H       H     H     OH     229     CH.sub.2CCH      OCH.sub.3                                      H     H     H     230     CH.sub.2CCH      H       H     H     OCH.sub.3     231     CH.sub.2CCH      OH      H     OCH.sub.3                                                  H     232     CH.sub.2CCH      H       OCH.sub.3                                            H     OH     233     CH.sub.2CCH      F       H     H     H     234     CH.sub.2CCH      H       H     F     H     235     CH.sub.2CCH      H       H     H     F     236     CH.sub.2CCH      Cl      H     H     H     237     CH.sub.2CCH      H       H     H     Cl     238     CH.sub.2CCH      H       H     H     Br     239     CH.sub.2CCH      CF.sub.3                                      H     H     H     240     CH.sub.2CCH      H       H     CF.sub.3                                                  H     241     CH.sub.2CCH      H       H     H     CF.sub.3     242     CH.sub.2CCH      H       OCH.sub.3                                            H     H     243     CH.sub.2CCH      H       H     OCH.sub.3                                                  H     244     CH.sub.2CCH      CN      H     H     H     245     CH.sub.2CCH      H       H     CN    H     246     CH.sub.2CCH      H       H     H     CN     247     allyl            F       H     H     H     248     allyl            H       F     H     H     249     allyl            H       H     F     H     250     allyl            H       H     H     F     251     allyl            Cl      H     H     H     252     allyl            H       Cl    H     H     253     allyl            H       H     Cl    H     254     allyl            H       H     H     Cl     255     allyl            Br      H     H     H     256     allyl            H       H     H     Br     257     allyl            Cl      H     H     Cl     258     allyl            H       Cl    H     Cl     259     allyl            H       Cl    Cl    H     260     allyl            F       H     H     F     261     allyl            H       F     H     F     262     allyl            H       F     F     H     263     allyl            OH      H     H     H     264     allyl            H       OH    H     H     265     allyl            H       H     OH    H     266     allyl            H       H     H     OH     267     allyl            OH      H     H     OH     268     allyl            OCH.sub.3                                      H     H     H     269     allyl            H       OCH.sub.3                                            H     H     270     allyl            H       H     OCH.sub.3                                                  H     271     allyl            H       H     H     H     272     allyl            OCH.sub.3                                      H     H     OCH.sub.3     273     allyl            OH      H     H     OCH.sub.3     274     allyl            OCH.sub.3                                      H     H     OH     275     allyl            OCH.sub.3                                      OCH.sub.3                                            H     OCH.sub.3     276     allyl            OH      OCH.sub.3                                            H     OCH.sub.3     277     allyl            OCH.sub.3                                      H     OCH.sub.3                                                  OCH.sub.3     278     allyl            OCH.sub.3                                      H     OCH.sub.3                                                  OH     279     allyl            OH      H     OCH.sub.3                                                  H     280     allyl            H       OCH.sub.3                                            H     OCH.sub.3     281     allyl            H       OCH.sub.3                                            H     OH     282     allyl            H       OCH.sub.2CH.sub.2 O                                                  H     283     allyl            H       OCH.sub.2O  H     284     allyl            H       OH    OH    H     285     allyl            SCH.sub.3                                      H     H     H     286     allyl            H       SCH.sub.3                                            H     H     287     allyl            H       H     SCH.sub.3                                                  H     288     allyl            H       H     H     SCH.sub.3     289     allyl                               ##STR32##                                      H     H     H     290     allyl            H       H     H                                                   ##STR33##     291     allyl            CH.sub.3                                      H     H     H     292     allyl            H       CH.sub.3                                            H     H     293     allyl            H       H     CH.sub.3                                                  H     294     allyl            H       H     H     H     295     allyl            CH.sub.3                                      H     H     CH.sub.3     296     allyl            CF.sub.3                                      H     H     H     297     allyl            H       CF.sub.3                                            H     H     298     allyl            H       H     CF.sub.3                                                  H     299     allyl            H       H     H     CF.sub.3     300     allyl            H       CH.sub.3                                            H     OH     301     allyl            OH      H     CH.sub.3                                                  H     302     allyl            H       C.sub.4 H.sub.4                                                  OH     303     allyl            H       C.sub.4 H.sub.4                                                  H     304     allyl            OH      C.sub.4 H.sub.4                                                  H     305     allyl            H       C.sub.4 H.sub. 4                                                   ##STR34##     306     allyl                               ##STR35##                                      C.sub.4 H.sub.4                                                  H     307     allyl            F       C.sub.4 H.sub.4                                                  OH     308     allyl            NO.sub.2                                      H     H     H     309     allyl            H       H     H     NO.sub.2     310     allyl            NH.sub.2                                      H     H     H     311     allyl            H       H     H     NH.sub.2     312     allyl                               ##STR36##                                      H     H     H     313     allyl            H       H     H                                                   ##STR37##     314     allyl            CN      H     H     H     315     allyl            H       CN    H     H     316     allyl            H       H     H     CN     317     allyl            C.sub.6 H.sub.5                                      H     H     H     318     allyl            H       C.sub.6 H.sub.5                                            H     H     319     allyl            H       H     C.sub.6 H.sub.5                                                  H     320     allyl            H       H     H     C.sub.6 H.sub.5     321     allyl            COOCH.sub.3                                      H     H     H     322     allyl            H       H     H     COOCH.sub.3     323     allyl            COOH    H     H     H     324     allyl            H       H     H     COOH     325     allyl            CONHCH.sub.3                                      H     H     H     326     allyl            H       H     H     CONHCH.sub.3     327     allyl            CON(CH.sub.3).sub.2                                      H     H     H     328     allyl            H       H     H     CON(CH.sub.3).sub.2     329     allyl            N(CH.sub.3).sub.2                                      H     H     H     330     allyl            H       H     H     N(CH.sub.3 .sub.2     331     allyl            F       H     H     NH.sub.2     332     allyl            NH.sub.2                                      H     H     F     __________________________________________________________________________

The active ingredients have a herbicidal action and are selective in crop plants.

The compounds, and herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions in the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples or surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyelene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 2 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 4 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

III. 20 parts by weight of compound no. 6 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

IV. 20 parts by weight of compound no. 59 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of compound no. 45 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.

VI. 3 parts by weight of compound no. 4 is intimately mixed with 97 parts by weight of particulate kaolin, A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 6 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 20 parts by weight of compound no. 59 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

The active ingredients or the herbicidal agents containing them may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.01 to 5.0, preferably 0.05 to 3.0, kg of active ingredient per hectare. The herbicidal action of the naphthindazoles of the formula I on the growth of test plants is illustrated by the following greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³ and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.

For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated. In this treatment method, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated with the compounds suspended or emulsified in water. The application rates for postemergence treatment were 0.5 and 1.0 kg/ha.

The pots were set up in the greenhouse, species from warmer climates in warmer areas (20° to 35° C.) and species from moderate climates at 10° to 20° C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed.

The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.

The plants used in the greenhouse experiments were Amaranthus retroflexus, Ipomoea spp., Setaria italica, Solanum nigrum and Veronica spp.

The compounds of Examples 2, 4 6, 45 and 59, applied postemergence at rates of 0.5, and 1.0 kg/ha, combated unwanted plants excellently.

In view of the number of application methods possible, the compounds according to the invention, or agents containing them, may be used in a further large number of crops for removing unwanted plants. The following crops are given by way of example:

    ______________________________________     Botanical name       Common name     ______________________________________     Allium cepa          onions     Ananas comosus       pineapples     Arachis hypogaea     peanuts (groundnuts)     Asparagus officinalis                          asparagus     Avena sativa         oats     Beta vulgaris spp. altissima                          sugarbeets     Beta vulgaris spp. rapa                          fodder beets     Beta vulgaris spp. esculenta                          table beets, red beets     Brassica napus var. napus                          rapeseed     Brassica napus var. napobrassica                          swedes     Brassica napus var. rapa                          turnips     Brassica rapa var. silvestris     Camellia sinensis    tea plants     Carthamus tinctorius safflower     Carya illinoinensis  pecan trees     Citrus limon         lemons     Citrus maxima        grapefruits     Citrus reticulata    mandarins     Citrus sinensis      orange trees     Coffea arabica (Coffea canephora,                          coffee plants     Coffea liberica)     Cucumis melo         melons     Cucumis sativus      cucumbers     Cynodon dactylon     Bermudagrass     Daucus carota        carrots     Elais guineensis     oil palms     Fragaria vesca       strawberries     Glycine max          soybeans     Gossypium hirsutum (Gossypium arbor-                          cotton     eum, Gossypium herbaceum, Gossypium     vitifolium)     Helianthus annuus    sunflowers     Helianthus tuberosus Jerusalem artichoke     Hevea brasiliensis   rubber plants      Hordeum vulgare     barley     Humulus lupulus      hops     Ipomoea batatas      sweet potatoes     Juglans regia        walnut trees     Lactuca sativa       lettuce     Lens culinaris       lentils     Linum usitatissimum  flax     Lycopersicon lycopersicum                          tomatoes     Malus spp.           apple trees     Manihot esculenta    cassava     Medicago sativa      alfalfa (lucerne)     Mentha piperita      peppermint     Musa spp.            banana plants     Nicotiana tabacum (N. rustica)                          tobacco     Olea europaea        olive trees     Oryza sativa         rice     Panicum miliaceum    millet     Phaseolus lunatus    limabeans     Phaseolus mungo      mungbeans     Phaseolus vulgaris   snapbeans, green beans,                          dry beans     Pennisetum g1aucum   pearl millet     Petroselinum crispum spp. tuberosum                          parsley     Picea abies          Norway spruce     Abies alba           fir trees     Pinus spp.           pine trees     Pisum sativum        English peas     Prunus avium         cherry trees     Prunus domestica     plum trees     Prunus dulcis        almond trees     Prunus persica       peach trees     Pyrus communis       pear trees     Ribes sylvestre      redcurrants     Ribes uva-crispa     gooseberries     Ricinus communis     castor-oil plants     Saccharum officinarum                          sugar cane     Secale cereale       rye     Sesamum indicum      sesame     Solanum tuberosum    Irish potatoes     Sorghum bicolor (s. vulgare)                          sorghum     Sorghum dochna       sorgo     Spinacia oleracea    spinach      Theobroma cacao     cacao plants     Trifolium pratense   red clover     Triticum aestivum    wheat     Triticum durum       durum wheat     Vaccinium corymbosum blueberries     Vaccinium vitis-idaea                          cranberries     Vicia faba           tick beans     Vigna sinensis (V. unguiculata)                          cow peas     Vitis vinifera       grapes     Zea mays             Indian corn, sweet corn,                          maize     ______________________________________

To increase the spectrum of action and to achieve synergistic effects, the naphthindazoles of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, (het)aryloxyphenoxypropionic acids and salts, esters and amides thereof, etc.

It may also be useful to apply the novel compounds of the formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added. 

We claim:
 1. A process for combating the growth of unwanted plants comprising: applying a herbicidally effective amount of a naphthindazole-4,9-quinone of the formula ##STR38## where: R¹ is hydrogen, C₁ -C₁₀ -alkyl, C₂ -C₁₀ -alkenyl, C₂ --C₁₀ -alkynyl, C₁ -C₁₀ -haloalkyl, C₁ -C₁₀ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, C₁ -C₄ -alkylcabonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, phenylaminocarbonyloxy-C₁ -C₄ -alkyl which is unsubstituted or substituted in the phenyl moiety by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, phenylsulfonyloxy-C₁ -C₄ -alkyl which is unsubstituted or substituted in the phenyl moiety by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl-C₁ -C.sub. -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl, di-(C₁ -C₄ -alkyl)-aminocarbonyl-C₁ -C₄ -alkyl, halo-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substituted heteroaryl radical with one or two nitrogen atoms, phenyl which is unsubstituted or substituted by halogen, hydroxy, nitro, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkylthio or C₁ -C₄ -haloalkylthio, or unsubstituted or halogen-substituted benzyl, andR², R³, R⁴ and R⁵ are identical or different and each denotes hydrogen, halogen, nitro, cyano, hydroxy, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkoxy, C₁ -C₅ -alkylthio, C₁ -C₅ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, carboxyl, C₂ -C₆ alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, C₂ -C₆ -haloalkanoyloxy, C₁ -C₄ -alkyl-carbonylamino, C₁ -C₄ -alkylaminocarbonyl, di-(C₁ -C₄ -alkyl)-aminocarbonyl, or phenyl or heteroaryl, each of which is unsubstituted or substituted by halogen, trifluoromethyl, nitro, cyano, amino, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio or C₁ -C₅ -haloalkylthio,and R³ and R⁴, together with the two carbon atoms of the phenyl ring to which they are attached, form a heterocyclic ring or a benzene or naphthalene ring which is unsubstituted or substituted by halogen, nitro, cyano, amino, hydroxy, trifluoromethyl, C₁ -C₅ -alkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkylthio, C₁ -C₅ -haloalkoxy or C₁ -C₅ -alkylthio,to unwanted plants and/or their habitat.
 2. A process as defined in claim 1, wherein R₁ of the naphthindazole-4,9-quinone is methyl and R², R³, R⁴ and R⁵ are each hydrogen.
 3. A process as defined in claim 1, wherein R¹ of the naphthindazole-4,9-quinone is 2-propenyl and R², R³, R⁴ and R⁵ are each hydrogen.
 4. A process as defined in claim 1, wherein R¹ of the napthindazole-4,9-quinone is methyl, R² is OH, and R³, R⁴ and R⁵ are each hydrogen.
 5. A process as defined in claim 1, wherein R¹ of the napthindazole-4,9-quinone is 1-methylethyl and wherein R², R³, R⁴ and R⁵ are each hydrogen.
 6. A process as defined in claim 1, wherein R¹ of the napthindazole-4,9-quinone is methyl, R², R³, and R⁵ are each hydrogen and wherein R⁴ is F. 